期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 50, 页码 26072-26079出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202107386
关键词
carbon dioxide reduction; hydrogen evolution; mechanism; photocatalysis; polypyridine metal complex
资金
- National Natural Science Foundation of China [22088102, 21933007, 21861132004, 21873031]
- Ministry of Science and Technology of China [2017YFA0206903]
- Strategic Priority Research Program of the Chinese Academy of Science [XDB17000000]
- Key Research Program of Frontier Sciences of the Chinese Academy of Science [QYZDY-SSW-JSC029]
The bis(pyridyl)amine-bipyridine-iron(II) framework (Fe(BPAbipy)) complexes 1-3 exhibit a multistep nature in CO2 reduction, with Fe-CO formation being the rate-determining step for selective CO2-to-CO reduction. Certain functional groups, such as the pendant alpha-OH group, play key roles in initiating H-2 evolution. This catalyst system shows promise for robust CO2 reduction by photocatalysis through advanced multi-electron and multi-proton transfer processes.
A bis(pyridyl)amine-bipyridine-iron(II) framework (Fe(BPAbipy)) of complexes 1-3 is reported to shed light on the multistep nature of CO2 reduction. Herein, photocatalytic conversion of CO2 to CO even at low CO2 concentration (1 %), together with detailed mechanistic study and DFT calculations, reveal that 1 first undergoes two sequential one-electron transfer affording an intermediate with electron density on both Fe and ligand for CO2 binding over proton. The following 2 H+-assisted Fe-CO formation is rate-determining for selective CO2-to-CO reduction. A pendant, proton-shuttling alpha-OH group (2) initiates PCET for predominant H-2 evolution, while an alpha-OMe group (3) cancels the selectivity control for either CO or H-2. The near-unity selectivity of 1 and 2 enables self-sorting syngas production at flexible CO/H-2 ratios. The unprecedented results from one kind of molecular catalyst skeleton encourage insight into the beauty of advanced multi-electron and multi-proton transfer processes for robust CO2RR by photocatalysis.
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